WO2013120550A1 - Sulfopolymer-containing liquid cleaning agent with low water content - Google Patents

Description

 Sulfopolymer-containing liquid detergent with low water content

The present invention relates to liquid detergents in a water-soluble packaging containing at least one sulfopolymer and at least one polyhydric alcohol, a process for its preparation and a method of use for automatic dishwashing detergents.

Consumers have come to comfortable dosing of pre-portioned machine

Dishwashing used and use these products especially in the form of tablets. On the other hand, liquid product forms in the form of multifunctional gels are increasingly gaining acceptance in the market. Above all, the rapid solubility and the associated rapid availability of the active ingredients offers advantages in particular in time-shortened

Washing programs. From the consumer's point of view, it is desirable to take advantage of both

To combine supply forms and to offer a pre-portioned liquid product.

In order to make a liquid dishwashing detergent into a pre-portioned form, the use of cold water-soluble films in the form of bags is common. Of the

However, there are limits to formula development since only a limited amount of water can be incorporated into the product. Exceeding the tolerable amount of water leads to premature dissolution of the enveloping water-soluble film.

In particular, the incorporation of polymers, which are essential for the good performance of a

Multifunktionsproduktes are, prepares in formulations that may only have small amounts of water, considerable difficulties.

Surprisingly, however, it has now been found that the incorporation of sulfopolymers into a detergent formulation is possible even with a small amount of water, in particular with a limitation of the amount of water to a maximum of 25 wt .-%, in particular to a maximum of 20 wt .-%, if at least one polyhydric alcohol contained in the composition.

A first subject of the present application is therefore a liquid detergent in a water-soluble packaging containing at least one sulfopolymer and at least one polyhydric alcohol.

The cleaning agent according to the invention is preferably a

Dishwashing agent, in particular a machine dishwashing detergent.

Another object of the present invention is also a machine

Dishwashing process, in which a detergent according to the invention is used. Another object of the present invention is a process for the preparation of liquid detergents in a water-soluble packaging, comprising at least one sulfopolymer and at least one polyhydric alcohol, wherein the sulfopolymer is used in solid form.

The amount of polyhydric alcohol or polyhydric alcohols used in detergents according to the invention is preferably at least 20% by weight, in particular at least 25% by weight, more preferably at least 28% by weight, especially at least 30% by weight. , Preferred quantitative ranges are in this case from 20 to 50% by weight, in particular from 25 to 45% by weight, in particular from 28 to 40% by weight.

The polyhydric alcohol is preferably selected from glycerol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and mixtures thereof.

In a preferred embodiment, a mixture of at least two polyhydric alcohols is used.

A polyhydric alcohol which is particularly preferably used according to the invention is 1,2-propylene glycol. 1,2-Propylene glycol is preferably used in inventive compositions in an amount of 1 to 40 wt .-%, in particular in an amount of 15 to 35 wt .-%, particularly preferably in an amount of 20 to 30 wt .-% ,

Another polyhydric alcohol particularly preferably used according to the invention is glycerol. Glycerol is used in inventive compositions preferably in an amount of 0, 1 to 15 wt .-%, in particular in an amount of 1 to 10 wt .-%, particularly preferably in an amount of 3 to 7 wt .-%, is used.

In a particularly preferred embodiment, a mixture of glycerol and 1, 2-propylene glycol is used.

The glycerol is preferably used here in an amount of 0.1 to 15% by weight, in particular in an amount of 1 to 10% by weight, more preferably in an amount of 3 to 7% by weight. The 1, 2-propylene glycol is in this case preferably in an amount of 1 to 40 wt .-%, in particular in an amount of 15 to 35 wt .-%, particularly preferably in an amount of 20 to 30 wt .-%, respectively to the total amount of the cleaning agent, the total amount of glycerol and 1,2-propylene glycol preferably being at least 20% by weight, in particular at least 25% by weight, especially at least 28% by weight, particularly preferably from 25 to 45% by weight, in particular from 28 to 40% by weight, especially from 28.5 to 32.0% by weight, is.

The liquid cleaning agent is preferably a water-containing

Composition. The water content of the composition of the invention is preferably at most 25 wt .-%, preferably below 20 wt .-%. preferred

Quantities are here 5 to 25 wt .-%, in particular 15 to 20 wt .-%, especially 18 to 19.8 wt .-%.

The proportion by weight of the sulfopolymer in the total weight of the invention

Cleaning agent is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12% by weight.

The sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.

The copolymers may have two, three, four or more different monomer units.

Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)

Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.

As unsaturated carboxylic acid (s) is / are used with particular preference unsaturated carboxylic acids of the formula R (R ² ) C = C (R ³ ) COOH, in which R to R ³ independently of -H, - CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or - COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl-acrylic acid, maleic acid,

Maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ^7, independently of one another, is -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH, or by -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, is straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH ( CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized

Sulfonsäuregruppenhaltigen copolymers is inventively preferred. The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of

Carboxylic acid-containing monomers 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ¹ , preferably from 4000 to 25,000 gmol ¹ and in particular from 5000 to 15,000 gmol ^"1 .

In another preferred embodiment, the copolymers include besides

Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer. The use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.

Detergent, characterized in that the agent comprises, as anionic copolymer, a copolymer comprising

 i) monomers containing carboxylic acid groups

 ii) sulfonic acid group-containing monomers

 iii) nonionic monomers, especially hydrophobic monomers

contains are preferred according to the invention.

As nonionic monomers are preferably monomers of the general formula

R (R ² ) C = C (R ³ ) -XR ⁴ used, in which R to R ^{3 are} independently -H, -CH ₃ or -C ₂ H ₅ , X is an optional spacer group selected is from -CH ₂ -, -C (0) 0- and -C (0) -NH-, and R ^{4 is} a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins of 10 or more Carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-α-olefin, 2-styrene, α-methylstyrene, 3-methylstyrene, 4-propylstryol, 4-cyclohexylstyrene, 4-dodecylstyrene, 2 Ethyl 4-benzylstyrene, 1-vinylnaphthalene, 2, vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate,

Hexyl acrylate, methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, A / - (2-ethylhexyl) acrylamide,

Octyl acrylate, octyl acrylate, A / - (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, A / - (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, A / - (stearyl) acrylamide, behenyl acrylate, Behenyl methacrylate and N- (behenyl) acrylamide or their mixtures.

The monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.

In a preferred embodiment of the invention, the liquid and water-containing cleaning agent according to the invention contains water to a maximum of 25 wt .-%, preferably up to 20 wt .-% in combination with sulfopolymer, which was used in the preparation of the agent in solid form. It was found that the homogeneous and stable incorporation of solid

Sulfopolymer then succeeds if at least one polyhydric alcohol is present in the agent.

In a further particularly preferred embodiment of the invention, the liquid and water-containing detergent water to a maximum of 25 wt .-%, sulfopolymer, which was used in the preparation of the agent in solid form, and as a polyhydric alcohol having a mixture of glycerol and propylene glycol.

The cleaning agent according to the invention is preferably contained in a water-soluble packaging. The water-soluble packaging allows a portioning of the cleaning agent. The amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.

The water-soluble packaging preferably comprises a water-soluble polymer. Some preferred water-soluble polymers which are preferably used as water-soluble packaging are polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones, Polyethylene oxides, celluloses and gelatin, wherein polyvinyl alcohols and acetalated polyvinyl alcohols are particularly preferably used.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

"Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, that is one more

Residual content of acetyl groups.

In the context of the present invention, it is preferred that the water-soluble packaging at least partly comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mole%. In a preferred embodiment, the water-soluble packaging consists of at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol, the Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%, is.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range from 5,000 to 100,000 gmol-1, preferably from 10,000 to 90,000 gmol-1, particularly preferably 12,000 to 80,000 gmol-1 and in particular from 15,000 to 70,000 gmol-1.

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and more preferably between about 260 to about 1500.

The water solubility of polyvinyl alcohol can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). As particularly preferred and have particularly advantageous because of their pronounced cold water solubility here

Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof. To use extremely advantageous are the reaction products of polyvinyl alcohol and starch. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.

The water-soluble packaging preferably has a thickness of 10 μιη to 500 μιη, in particular from 20 μιη to 400 μιη, more preferably from 30 μιη to 300 μιη, especially from 40 μιη to 200 μιη, in particular from 50 μιη to 150 μιη.

An especially preferred polyvinyl alcohol is, for example, under the

Trade name M8630 (Monosol) available.

The viscosity of cleaning agents according to the invention is preferably above 4000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C.), in particular between 4000 and 7000 mPas, more preferably between 4500 and 6500 mPas, especially between 5000 and 6000 mPas.

The pH of cleaning agents according to the invention is preferably between 6 and 10, more preferably between 7 and 9, especially between 7 and 8.

Detergents according to the invention preferably further comprise at least one

nonionic surfactant. As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.

Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH ₂ O- (AO) _w - (AO) _x - (A "O) _y - (A" O) _z -R ² , in which

R stands for a straight-chain or branched, saturated or mono- or polyunsaturated _C6 -24 alkyl or alkenyl group; R ^{2 is} hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

A, Α ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ "CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, - CH ₂ -CH (CH ₂ -CH ₃ ),

 w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0,

are preferred.

By the addition of the aforementioned nonionic surfactants of the general formula R - CH (OH) CH ₂ O- (AO) w - (AO) _x - (A "O) _y - (A '" O) _z -R ² , hereinafter also As "hydroxymix ether", surprisingly, the cleaning performance of inventive compositions can be significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

By using these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the detergent formulations according to the invention can be markedly improved.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 0 [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R which is linear or branched, saturated or unsaturated, aliphatic or aromatic

Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22

Carbon atoms, furthermore a linear or branched, saturated or

unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30

Have carbon atoms, wherein x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particular preference is given to surfactants of the formula R 0 [CH ₂ CH (CH 3) O] _x [CH ₂ CH ₂ O] _y CH ₂ Cl-1 (OI-l) R ² in which R is a linear or branched aliphatic hydrocarbon radical 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched

Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.

The group of these nonionic surfactants include, for example, the C ₂ -26 fatty alcohol (PO) i (EO) i ₅ . 4o-2-hydroxyalkyl ethers, in particular also the C ₈ -io-fatty alcohol (PO) i (EO) ₂₂ -2-hydroxydecyl ethers.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) Nonionic surfactants of the formula R 0 [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R and R ² independently of one another represent a linear or branched, saturated or - or several times

unsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y independently represent values between 1 and 32, with nonionic surfactants with R ³ = -CH ₃ and values for x of 15 to 32 and y of 0.5 and 1.5 being very particularly preferred.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R and R ² for linear or branched, saturated or unsaturated, aliphatic or aromatic

Hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the above formula

R 0 [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 be} different. R and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic

Hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO),

(PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula zu

R 0 [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R, R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R and R ² Have 9 to 14 carbon atoms, R ^{3 is} H and x assumes values of 6 to 15. Finally, the nonionic surfactants of the general formula R -CH (OH) CH ₂ O- (AO) _w -R ^{2 have} proved to be particularly effective, in which

 R for a straight-chain or branched, saturated or on or

polyunsaturated _C6 -24 alkyl or alkenyl radical;

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26

Carbon atoms;

A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ),

preferably CH ₂ CH ₂ , and

 w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The group of these nonionic surfactants include, for example, the C 4-22 fatty alcohol (EO) i ₀ -8o-2-hydroxyalkyl ethers, in particular also the C ₈ -12 fatty alcohol (EO) ₂ 2-2-hydroxydecyl ethers and the C ₄ . 22 fatty alcohol (EO) ₄₀ -8o-2-hydroxyalkyl ethers.

Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant on

Total weight of the cleaning agent is preferably 0.5 to 10 wt .-%, preferably 1, 0 to 8.0 wt .-% and in particular 2.0 to 6.0 wt .-%.

As a further constituent cleaning agents according to the invention preferably contain one or more builder (s). The proportion by weight of these builders in the total weight

Inventive agent is preferably 15 to 80 wt .-% and in particular 20 to 70 wt .-%. These builders include in particular carbonates, phosphates, citrates,

Phosphonates, MGDA, GLDA, EDDS, organic cobuilders and silicates.

Preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali carbonate (s), more preferably sodium carbonate, in amounts of 2 to 30 wt .-%, preferably from 4 to 28 wt .-% and in particular from 8 to 24 wt .-%, each based on the weight of the cleaning agent.

Preference is also the use of phosphate. Among the large number of commercially available phosphates, the alkali metal phosphates have, with particular preference of pentasodium or. Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the washing and

Detergent industry the biggest importance.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids in which one Metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 ₄ can distinguish in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na ₅ P ₃ Oi ₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ Oi ₀ (potassium tripolyphosphate). The sodium-potassium tripolyphosphates are also preferably used according to the invention.

If phosphates are used as cleaning-active substances in the cleaning agents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the cleaning agent.

In a preferred embodiment according to the invention, the use of phosphates is largely or completely omitted. The agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s). Particularly preferably, the agent is completely phosphate-free in this embodiment.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,

Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof. In addition to their builder action, the free acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of cleaning agents. In particular, here are citric acid,

Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof. Particularly preferred cleaning agents according to the invention contain citrate as one of their essential builders. Detergents, characterized in that they contain 2 to 40 wt .-%, preferably 5 to 30 wt .-% and in particular 5 to 20 wt .-% citrate, are inventively preferred.

Particularly preferred cleaning agents according to the invention are characterized in that the cleaning agent contains at least two builders from the group of phosphates, carbonates and citrates, wherein the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, preferably 5 to 60 wt .-%, preferably 15 to 50% by weight and especially 25 to 40% by weight. The combination of two or more builders from the above group has favored the cleaning and rinse performance

Automatic dishwashing detergent according to the invention has proven to be advantageous.

In a very particularly preferred embodiment according to the invention, a mixture of phosphate and citrate or a mixture of GLDA and citrate is used, the amount of phosphate or GLDA preferably being from 10 to 35% by weight and the amount of citrate preferably from 2 to 10% by weight .-%, in each case based on the total amount of the cleaning agent, is, wherein the total amount of these builders is preferably 20 to 35 wt .-%, in particular 25 to 35 wt .-%, is.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

The content of (homo) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.

The cleaning agents according to the invention can be used as further builder in particular

Contain phosphonates. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are in agents according to the invention preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.

At least one compound selected from MGDA, GLDA and EDDS is preferably used, in particular in phosphate-reduced and phosphate-free compositions.

MGDA (methylglycinediacetic acid), GLDA (glutamic acid-N, N-diacetic acid) and EDDS

(Ethylenediamine-N, N'-disuccinic acid) are preferably used in detergents according to the invention in amounts of 5 to 60 wt .-%, in particular in amounts of 10 to 40 wt .-%.

Agents of the invention can be used as builder also crystalline layered silicates of general formula NaMSi _x 0 _{2x +} i ^■ y H ₂ 0 wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

In preferred cleaning agents according to the invention, the content of silicates, based on the total weight of the cleaning agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred cleaning agents according to the invention are silicate-free.

In addition to the abovementioned builders, the agents according to the invention may contain alkali metal hydroxides. These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of

Detergent used. Alternative cleaning agents according to the invention are free of alkali metal hydroxides.

As a further constituent cleaning agents according to the invention preferably contain enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are correspondingly preferred be used. Detergents according to the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in detergents developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens

(DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, those originally from Humicola lanuginosa

(Thermomyces lanuginosus) available, or further developed lipases, especially those with the amino acid exchange D96L.

Furthermore, enzymes can be used which are termed hemicellulases

be summarized. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferable to add organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the

Stains to ensure the flow of electrons (mediators). A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations. Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or

Chemical-impermeable protective layer is coated. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric

Film former, low-dust and storage-stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

As can be seen from the previous comments, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and

in particular between 0.8 and 10% by weight of the enzyme protein. Preference is given in particular to those detergents which, in each case based on their

Total weight, 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations.

Compositions according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaching agents, bleach activators, bleach catalysts, further solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular

Silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances and antimicrobial agents.

As a further solvent agents according to the invention preferably contain at least one alkanolamine. The alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.

Zinc salts are preferably used as glass corrosion inhibitors.

Glass corrosion inhibitors are preferably present in agents according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.

Examples

Three liquid detergents with water contents below 20% by weight were prepared (E1 and V1 and V2), water or an aqueous phosphate solution being initially charged and the sulfopolymer being added in each case in solid form to the liquid mixture.

Table 1: Quantities in% by weight

Only the agent E1 according to the invention could be prepared without difficulty and stably, while in V1 and V2 the incorporation of the solid sulfopolymer already failed.

Claims

claims 1. Liquid detergent in a water-soluble packaging containing at least one sulfopolymer and at least one polyhydric alcohol. 2. Cleaning agent according to claim 1, characterized in that it contains 20 to 50 wt .-%, in particular 25 to 45 wt .-%, especially 28 to 40 wt .-%, of polyhydric alcohols, in particular selected from glycerol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and mixtures thereof. 3. Cleaning agent according to claim 1 or 2, characterized in that it as  polyhydric alcohol 1, 2-propylene glycol, preferably in an amount of 15 to 35 wt .-%, particularly preferably in an amount of 20 to 30 wt .-%. 4. Cleaning agent according to claim 3, characterized in that it contains a mixture of glycerol and 1, 2-propylene glycol, wherein the glycerin in an amount of 1 to 10 wt .-%, preferably 3 to 7 wt .-%, and the 1, 2-propylene glycol in an amount of 15 to 35 wt .-%, preferably 20 to 30 wt .-%, each based on the total amount of the cleaning agent, is used, wherein the total amount of glycerol and 1, 2-propylene glycol 25 bis 45 wt .-%, in particular 28 to 40 wt .-%, especially 28.5 to 32.0 wt .-%, is. 5. Cleaning agent according to one of the preceding claims, characterized in that the composition is at most 25 wt .-% water, preferably at most 20 wt .-%, in particular 15 to 20 wt .-%, and particularly preferably 18 to 19.8 wt. -% water, contains. 6. Cleaning agent according to one of the preceding claims, characterized in that it contains sulfopolymer, which was used in the preparation of the agent in solid form. 7. Cleaning agent according to one of the preceding claims, characterized in that it is a polyvinyl alcohol-containing film in the water-soluble packaging. 8. Cleaning agent according to one of the preceding claims, characterized in that comprising as a sulfopolymer, a polymer i) monomers containing carboxylic acid groups, ϋ) monomers containing sulfonic acid groups,  Iii) optionally nonionic, in particular hydrophobic, monomers  is used, wherein the total amount of sulfopolymer is preferably 1 to 15 wt .-%, in particular 4 to 14 wt .-%, especially 6 to 12 wt .-%. 9. Cleaning agent according to one of the preceding claims, characterized in that it contains at least one hydroxymix ether, wherein the total amount of hydroxy mixed ether preferably 0.5 to 10 wt .-%, in particular 1, 0 to 8.0 wt .-%, particularly preferably 2.0 to 6.0 wt .-%, is. 10. Cleaning agent according to one of the preceding claims, characterized in that it has a viscosity above 4000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 4000 and 7000 mPas, more preferably between 4500 and 6500 mPas, especially between 5000 and 6000 mPas. 1 1. A process for the preparation of a liquid cleaning agent in a water-soluble  Packaging according to one of claims 1 to 10, characterized in that the sulfopolymer is used in solid form. 12. A machine dishwashing process, characterized in that a cleaning agent according to one of claims 1 to 10 is used.